Electrocatalyst groups

In addition to these different types of alloys, some studies were also devoted to alternatives to platinum as electrocatalysts. Unfortunately, it is clear that even if some catalytic activities were observed, they are far from those obtained with platinum. Nickel tungsten carbides were investigated, but the electrocatalytic activity recorded for methanol oxidation was very low. Tungsten carbide was also considered as a possible alternative owing to its ability to catalyze the electrooxidation of hydrogen. However, it had no activity for the oxidation of methanol and recently some groups showed that a codeposit of Pt and WO3 led to an enhancement of the activity of platinum. ... 

Significant (and even spectacular) results were contributed by the group of Norskov to the field of electrocatalysis [102-105]. Theoretical calculations led to the design of novel nanoparticulate anode catalysts for proton exchange membrane fuel cells (PEMFC) which are composed of trimetallic systems where which PtRu is alloyed with a third, non-noble metal such as Co, Ni, or W. Remarkably, the activity trends observed experimentally when using Pt-, PtRu-, PtRuNi-, and PtRuCo electrocatalysts corresponded exactly with the theoretical predictions (cf. Figure 5(a) and (b)) [102]. 

Numerous metal complexes have been proven to be active electrocatalysts for C02 reduction.1,66-68 These catalysts can be conveniently grouped into three main families metal complexes with polypyridyl ligands, metal complexes with macrocyclic ligands, and metal complexes with phosphorus ligands. 

Furthermore, the utilization of preformed films of polypyrrole functionalized by suitable monomeric ruthenium complexes allows the circumvention of problems due to the moderate stability of these complexes to aerial oxidation when free in solution. A similar CO/HCOO-selectivity with regards to the substitution of the V-pyrrole-bpy ligand by an electron-with-drawing group is retained in those composite materials.98 The related osmium-based redox-active polymer [Os°(bpy)(CO)2] was prepared, and is also an excellent electrocatalyst for the reduction of C02 in aqueous media.99 However, the selectivity toward CO vs. HCOO- production is lower. 

In view of the complexity of heterogeneous systems, none of the above techniques will be able to supply, by itself, a complete atomic-level description of surface phenomena. A multi-technique approach has been perceived by many as most appropriate for fundamental studies in electrochemical surface science (30-2). Since none of the existing electrochemical laboratories are adequately equipped to perform a comprehensive experimental study, collaborative efforts between research groups of different expertise are burgeoning. Easier access to national or central facilities are also being contemplated for experiments which cannot be performed elsewhere. The judicious combination of the available methods in conjunction with the appropriate electrochemical measurements are permitting studies of electrocatalyst surface phenomena unparalleled in molecular detail. 

The elemental composition, oxidation state, and coordination environment of species on surfaces can be determined by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) techniques. Both techniques have a penetration depth of 5-20 atomic layers. Especially XPS is commonly used in characterization of electrocatalysts. One common example is the identification and quantification of surface functional groups such as nitrogen species found on carbon-based catalysts.26-29 Secondary Ion Mass spectrometry (SIMS) and Ion Scattering Spectroscopy are alternatives which are more surface sensitive. They can provide information about the surface composition as well as the chemical bonding information from molecular clusters and have been used in characterization of cathode electrodes.30,31 They can also be used for depth profiling purposes. The quantification of the information, however, is rather difficult.32... 

PB and its derivatives are of interest for a variety of reasons, the most important of which is its electrochromism [93]. In addition, it is an electrocatalyst for several different types of substrates, notably hydrogen peroxide, as will be seen below. Synthesis of nanopartides of Prussian Blue is relatively straightforward. It relies on many of the prindples of colloid chemistry, and produces ionically stabilized colloidal solutions (Figure 4.7). As a consequence, the electrochemical behavior of PB N Ps has been examined by several groups. In this section, we discuss the behavior of P B N Ps immobilized at electrodes. 

Fig. 3. Schematic illustration of the synthesis of metal nanoparticles within dendrimer templates. The composites are prepared by mixing of the dendrimer and metal ion, and subsequent chemical reduction. These materials can be immobilized on electrode surfaces where they serve as electrocatalysts or dissolved in essentially any solvent (after appropriate end-group functionalization) as homogeneous catalysts for hydrogenation and other reactions...

It is intriguing that analysis of the volcano curve predicts that the apex of the curve occurs at AH(H2)ads = 0 (formally, AG = 0) [26]. This value corresponds to the condition D(M-H) = 1/2D(H-H), that is, forming an M-H bond has the same energetic probability as forming an H2 molecule. This condition is that expressed qualitatively by the Sabatier principle of catalysis and corresponds to the situation of maximum electrocatalytic activity. Interestingly, the experimental picture shows that the group of precious transition metals lies dose to the apex of the curve, with Pt in a dominant position. It is a fact that Pt is the best catalyst for electrochemical H2 evolution however, its use is made impractical by its cost. On the other hand, Pt is the best electrocatalyst on the basis of electronic factors only, other conditions being the same. 

The values obtained in different laboratories for the activity of various electrocatalysts are not directly comparable. The reduction of oxygen — for which data have been published by various groups — proceeds at the three-phase boundary where gas, liquid, and solid meet. This boundary is affected by such macroscopic properties of the catalyst as particle size, density, surface tension, and porosity. 

This section presents a short survey of the results published by various groups working on organic electrocatalysts for the cathodic reduction of oxygen. Widely differing experimental techniques have been used. The difficulty of quantitative comparison of the activities of different catalysts has been mentioned (Section 2.2). 

In the most important series of polymers of this type, the metallotetraphenylporphyrins, a metalloporphyrin ring bears four substituted phenylene groups X, as is shown in 7.19. The metals M in the structure are typically iron, cobalt, or nickel cations, and the substituents on the phenylene groups include -NH2, -NR2, and -OH. These polymers are generally insoluble. Some have been prepared by electro-oxidative polymerizations in the form of electroactive films on electrode surfaces.79 The cobalt-metallated polymer is of particular interest since it is an electrocatalyst for the reduction of dioxygen. Films of poly(trisbipyridine)-metal complexes also have interesting electrochemical properties, in particular electrochromism and electrical conductivity.78 The closely related polymer, poly(2-vinylpyridine), also forms metal complexes, for example with copper(II) chloride.80... 

In summary, the electrochemical results indicate that the alkyl-metal bond-formation free energies range from 54 to 146 kJ mol-1 for iron porphyrins and from 84 to 159 kJ mol-1 for cobalt porphyrins. The maximum bond energies are for primary alkyl groups bonded to [(MeO)4TPP]Con and (OEP)Fen porphyrins. The porphyrin dianions [(porT)nFe and (porr)nCo ] facilitate the reduction of C02 to CO via the transient formation of a metal-carbon bond [(por7)M—C(0)0- — AGBF > 50 kJ mol-1 for iron porphyrins]. Thus, iron and cobalt porphyrins are especially effective electrocatalysts for the reduction of C02 ... 

The example considered is the redox polymer, [Os(bpy)2(PVP)ioCl]Cl, where PVP is poly(4-vinylpyridine) and 10 signifies the ratio of pyridine monomer units to metal centers. Figure 5.66 illustrates the structure of this metallopolymer. As discussed previously in Chapter 4, thin films of this material on electrode surfaces can be prepared by solvent evaporation or spin-coating. The voltammetric properties of the polymer-modified electrodes made by using this material are well-defined and are consistent with electrochemically reversible processes [90,91]. The redox properties of these polymers are based on the presence of the pendent redox-active groups, typically those associated with the Os(n/m) couple, since the polymer backbone is not redox-active. In sensing applications, the redox-active site, the osmium complex in this present example, acts as a mediator between a redox-active substrate in solution and the electrode. In this way, such redox-active layers can be used as electrocatalysts, thus giving them widespread use in biosensors. 

NADPH and NADH are closely related structurally, differing only by the addition of a phosphate group to the ribose sugar of NADH. One would expect, therefore, that a film which was a good electrocatalyst for... 

Tungsten carbide — WC, belongs to a class of Group IV B-VIB transition metal carbides and nitrides, often referred to as interstitial alloys, in which the carbon and nitrogen atoms occupy the interstitial lattice positions of the metal [i]. These compounds possess properties known from group VIII B precious metals like platinum and palladium [ii]. Thus, they show remarkable catalytic activities, attributed to a distinct electronic structure induced by the presence of carbon or nitrogen in the metal lattice. Tungsten carbide resembles platinum in its electrocatalytic oxidation activity (- electrocatalysis) and is therefore often considered as an inexpensive anode electrocatalyst for fuel cell [iii] and -> biofuel cell [iv] application. 

An alternative to using commercially available carbon for electrocatalyst carbon substrates is to build a specific carbon structure having controlled properties. Thus, carbons have been prepared by the controlled pyrolysis of polyacrylonitrile (PAN) and contain surface nitrogen groups that act as peroxide decomposing agents.62... 

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